Low shrink low density laminate formulation

ABSTRACT

Composite articles are prepared by a spray up operation. In a first step, a gel coat is applied onto a mold surface which has been optionally pretreated with a mold release coating. Next, a barrier coat is applied over the gel coat in the mold and thereafter a laminate formula is applied over the barrier coat. The laminate contains from 40-80% by weight paste and from 20-60% by weight reinforcing fibers. In a preferred embodiment, the paste comprises 90% or more by weight resin, up to 5% filler, and an initiator composition capable of initiating cure at a temperature of 50° C. or lower. In a preferred embodiment, the multilayer composite has a thickness of about 15 mm or less, and is useful as an automobile body panel. The laminate preferably comprises a low shrink, low density glass fiber filled polyester resin. In a preferred embodiment, the paste of the laminate contains a dicyclopentadiene unsaturated polyester resin, polymeric hollow microspheres, and an initiator capable of initiating curing at room temperature or at temperature of 50° C. or less.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. provisional applications 60/400,095 and 60/400,324, both of which were filed on Aug. 1, 2002, the disclosures of both of which are incorporated by reference.

FIELD OF THE INVENTION

[0002] The present invention generally relates to composite materials containing fiber reinforced cured polyester resins as a structural layer. More particularly, the invention relates to methods of manufacturing such articles by open tool molding for use as light-weight composites for automobile body panels.

BACKGROUND OF THE INVENTION

[0003] Light-weight composites are commonly used in manufacturing cars with lighter weight and improved fuel economy. The composites are currently produced using expensive steel tools and technologically advanced compression molding machines.

[0004] Open tool molding is a process for producing relatively low cost composite panels at low volumes. While steel molds are often used for other molding operations, the open tool molding process was developed to use less expensive one-sided epoxy or polyester molds to produce various products, such as composite panels with an in-mold finish.

[0005] Alternative methods of producing light weight composites can be utilized. Open tool molding is an example of such a method. To obtain a reasonable surface appearance, the process requires the use of a gel coat followed by a supporting composite laminate. In the process, a mold surface is first cleaned, a mold release coating is optionally applied, and a layer of a gel coat is applied and partially cured. A laminate is then applied to the gel coat layer, and the laminate and gel coat are cured to form a unitary part having a surface defined by the cured gel coat. Molded parts can be produced by this method to have a finish bearing any desired color originally carried by the gel coat.

[0006] In some applications, in order to obtain a smooth surface finish on the gel coat and reduce the extent of fiber read through, a barrier coat may be applied between the gel coat and the laminate. It would be desirable to produce low density, low shrink laminate for use in such processes.

SUMMARY OF THE INVENTION

[0007] In one aspect, the invention provides a method for preparing a composite article by spray up operation. In a first step, a gel coat is applied onto a mold surface which has been optionally pretreated with a mold release coating. Next, a barrier coat is applied over the gel coat in the mold and thereafter a laminate formula is applied over the barrier coat. The laminate contains from 40-80% by weight paste and from 20-60% by weight reinforcing fibers. In a preferred embodiment, the paste comprises 90% or more by weight resin, up to 5% filler, and an initiator composition capable of initiating cure at a temperature of 50° C. or lower. In a preferred embodiment, the multilayer composite has a thickness of about 4 mm or less, and is useful as an automobile body panel.

[0008] The laminate preferably comprises a low shrink, low density glass fiber filled polyester resin. In a preferred embodiment, the paste of the laminate contains a dicyclopentadiene unsaturated polyester resin, polymeric hollow microspheres, and an initiator capable of initiating curing at room temperature or at temperature of 50° C. or less.

[0009] In another aspect, an automobile body panel is provided comprising a gel coat layer, a laminate layer, and a barrier layer disposed between the gel coat and the laminate layer. The laminate layer contains reinforcing glass fibers and a matrix of a cured polyester resin. The matrix can contain up to 5% by weight of polymeric hollow microspheres.

[0010] Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:

[0012]FIG. 1 is a diagram of a three layer composite of the invention in a mold;

[0013]FIG. 2 is a diagram of a three layer composite of the invention after a release from the mold.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.

[0015] Composite articles of the invention comprise a gel coat layer, a laminate layer, and a barrier layer disposed between the gel coat and the laminate. FIG. 1 illustrates schematically a composite of the invention in a mold. A three-layer composite is shown in contact with a surface of a mold 12. A gel coat layer 14 is applied directly to the mold surface. A barrier coat 16 is applied on top of the gel coat 14. A laminate layer 18 is applied on top of the barrier coat 16. An optional mold release layer (not shown) may be applied between the mold surface 12 and the gel coat layer 14.

[0016]FIG. 2 shows in schematic form a composite 20 of the invention. Three layers are shown: a laminate layer 18, a barrier coat 16, and gel coat 14.

[0017] The laminate layer, described further below, is made of a cured polyester resin containing reinforcing fibers. The laminate layer provides most of the strength of the composite article. The gel coat layer may be pigmented. It is used to provide an esthetic appearance to the composite article. The barrier coat situated between the gel coat and the laminate provides protection from fiber read through. As such, it contributes to the esthetic appearance of the gel coat layer.

[0018] Composites of the invention are generally made by sequentially applying into a mold the various layers of the composite. After an optional mold release layer is applied, a gel coat is first applied into a mold. Thereafter a barrier coat is applied over the gel coat and a laminate is applied over the barrier coat. Each layer may consist of one or more separate layers. In a preferred embodiment, the gel coat and the barrier coat are sprayed into the mold. In one aspect, each pass of the spray gun may be thought of as applying a thin layer. The effect of several passes of the spray gun used to apply the layers is to produce a built up gel coat or barrier coat layer as shown in the figures.

[0019] Similarly, the laminate layer may be sprayed on top of the barrier coat in a series of layers or passes with a spray gun. Alternatively, the laminate layer may be applied in a series of hand lay up steps wherein a glass mat is first installed in the mold over the barrier coat and then a paste formula is sprayed over the glass mat to wet out the glass and form the laminate layer.

[0020] The composite articles made according to the invention can have a range of thicknesses. Preferably, the laminate layer is thick enough to provide the needed stiffness, strength, or rigidity necessary for the application or end use of the composite article. In a preferred embodiment, the composites serve as automobile body panels. In this embodiment, the thickness of the composite article ranges from about 2 mm up to about 15 mm, preferably up to about 12 mm. More preferably, the thickness is from 3-8 mm. Of this, the gel coat is preferably from about 0.5-1.5 mm thick, the barrier coat from about 0.25 to 2 mm thick and the laminate layer from about 1 to about 5 mm thick.

[0021] The composite article is cured before release from the mold. Curing may continue in the demolded article. In preferred embodiments, the individual layers are partially cured after application before the next layer is applied. For example, a gel coat may be applied to a mold and partially cured. Thereafter the barrier coat is applied and again the gel coat and barrier coat are partially cured in the mold. Finally, a laminate layer is applied on top of the barrier coat and the composite article of the invention is cured. Curing is preferably carried out at low temperatures, for example at room temperature or at less than about 50° C.

[0022] Gel coats for use in molded plastic articles are well known in the art. The gel coats of the invention typically contain a curable thermosetting organic resin. In a preferred embodiment, the gel coat contains a pigment to provide color to a surface of the molded article. Generally, the gel coat can contain any type of organic resin capable of curing into a coating layer. Without limitation, the gel coat may include polyurethane resins, polyester resins, epoxy resins, acrylic resins, and the like. They may also contain secondary or crosslinking resins such as acrylic resins, aminoplasts, and hydroxyl resins. The gel coat may contain resins that crosslink with themselves upon curing to form the coating, or they may contain one or a plurality of second resins with complementary functional groups that react with one another to form a crosslinked cured composition.

[0023] The barrier coats for use with the laminates of the invention are described below and in Assignee's provisional application 60/400,324, filed Aug. 1, 2002, entitled “Barrier Coat for Open Tool Molding”.

[0024] The barrier coat typically contains an unsaturated polyester resin. As such it contains hydroxyl groups that are capable of binding either covalently or via hydrogen bonds to functional groups of the gel coat, resulting in good interlayer adhesion. Preferably, the barrier coat provides enough flexibility to avoid cracking along with sufficient rigidity to shield the gel coat from the effects of any shrinkage that the laminate structure undergoes upon cure. The stiffness of the barrier coat, which is a combination of its rigidity and its thickness, mitigates against fiber read through. The fiber read through is observed in gel coats directly coating fiber reinforced laminate layers. For automobile panels, the resulting fiber read through generally results in undesirable surface appearance in the gel coat. The barrier coats of the invention are applied in part to minimize the fiber read through. In a preferred embodiment, the barrier coat contains glass fibers having a length of 1 mm or less, preferably having a length of 0.5 mm or less.

[0025] Another function of the barrier coating is to separate the shrinkage of the laminate layer from the gel coat and prevent the shrinkage from harming the esthetic properties of the gel coat surface. The barrier coat should be flexible enough so as not to crack under those conditions and have enough rigidity to support the gel coat. Flexibility is generally reflected in the property of tensile elongation at break, such as is measured with ASTM method D-638. It has been found that a tensile elongation at break of 0.5% or less is indicative of a barrier coat that is too brittle. Preferably the tensile elongation at break of the barrier coat is at least 1% and preferably about 2% or greater. In a preferred embodiment, a tensile elongation of 2-3% has been found acceptable.

[0026] In a preferred embodiment, short reinforcing fibers are added to the barrier composition to increase the strength and modulus. In a typical composition, the flexural modulus is about 1900 MPa and the tensile modulus is about 1896 MPa.

[0027] Reinforcing fibers for the barrier coat may be selected from glass fibers, carbon fibers, and ceramic fibers. In a preferred embodiment, glass fibers are used for convenience. The invention will be further described and exemplified by reference to glass fibers.

[0028] The length of the glass fibers in the barrier coat is preferred to be less than the length of the fibers in the laminate coat. In a preferred embodiment, the glass fibers in the barrier coat are of such a length that they may be readily sprayed with conventional spray equipment. Thus, glass fibers no longer than about 0.5 mm in length—the size of a nozzle of conventional spray equipment—are preferred. In a preferred embodiment, the glass fibers are of a diameter of 5-10 micrometers.

[0029] Milled glass fibers are commercially available having lengths of less than about 0.5 mm. In a preferred embodiment, milled glass fibers of {fraction (1/64)} inch (about 0.4 mm) are formulated into the polyester resin of the barrier coat formulation. In another preferred embodiment, milled glass fibers having a length of about 0.001 inch (about 0.025 mm) are used. It is believed that the presence of the milled glass fibers in the barrier coat also contributes to the property of reducing or eliminating fiber read through from the laminate to the gel coat.

[0030] Other reinforcing fibers, such as ceramic fibers or carbon fibers can also be used in the barrier coat to provide the favorable properties. However, glass fibers are usually preferred, for example because of lower costs. Preferably, the fibers in the barrier coat provide the barrier coat with enough flexibility and strength to avoid cracking during demolding and handling.

[0031] To achieve the desired flexibility, the barrier coat contains a flexible polyester resin. Preferably, the polyester resin of the barrier coat comprises up to 25% of an isophthalic resin, based on the total weight of the polyester resin. In a preferred embodiment, the polyester resin comprises 75-100% and preferably 75-99% by weight of a dicyclopentadiene resin. That is, in a preferred embodiment, the polyester resin of the barrier coat contains a major part of a dicyclopentadiene resin and at least one other resin. In a preferred embodiment, the polyester resin of the barrier coat comprises dicyclopentadiene resin and an isophthalic acid resin in ratio of at least 4:1. It has been found that barrier coats with such polyester resin compositions can achieve the desired flexibility of a tensile elongation of at least about 1% at break, as measured by ASTM D-638. In a preferred embodiment, the resin component of the barrier coat composition contains 80-100 parts of dicyclopentadiene resin and up to 20 parts isophthalic acid resin.

[0032] The laminate layer of the invention contains from about 40-80% by weight of a paste and from 20-60% by weight of reinforcing fibers. The paste contains, by percent based on the total weight of the paste, 70% or more of an unsaturated polyester resin curable at a temperature of 50° C. or lower, up to 25% of a filler comprising particles having a density lower than that of the resin, and an initiator composition capable of initiating cure of the resin at a temperature of 50° C. or lower. The polyester resin of the laminate layer is preferably a low shrink resin, exhibiting a volume shrinkage upon cure of less than about 9.6%, preferably 9% or less and more preferably about 8% or less. In a preferred embodiment, the polyester resin of the laminate layer comprises a dicyclopentadiene unsaturated polyester resin. The structure and synthesis of the polyester resins are discussed further below.

[0033] The filler comprising particles having a density lower than that of the resin preferably comprises hollow microspheres, also known as micro balloons or micro bubbles. Typically, they range in size from about 5 to about 200 microns, with a wall thickness between about 0.4 and 1.5 microns. They generally have a density in the range of from about 0.03 to about 0.5 g/cm³. The microspheres are used to reduce the density of the layer in which they found by displacing some of the resin with air that is encapsulated in the thin wall spheres.

[0034] The microspheres are made from material particles by heating them in the presence of blowing agents. The microspheres may be hollow glass microspheres, hollow ceramic microspheres, hollow polymeric microspheres, hollow carbon microspheres, or combinations of them. Hollow polymeric microspheres can be prepared from an aqueous suspension or solution of a film forming resin and a blowing agent. The blowing agents are typically low boiling point hydrocarbons or inorganic or organic material that decomposes to provide a blowing agent.

[0035] When glass hollow microspheres are used as the filler, they may comprise up to about 25% by weight of the paste. Polymeric hollow microspheres are lighter than the glass hollow microspheres. Accordingly, when polymeric hollow microspheres are used, it is preferred to use them at a level up to 5% by weight of the paste. In a preferred embodiment, the paste contains 90% or more by weight unsaturated polyester resin and up to 5% by weight polymeric hollow microspheres. In a preferred embodiment, the unsaturated polyester resin is a low shrink resin such as a dicyclopentadiene resin discussed below. Glass and polymeric microspheres may also be used together. In such a case, the polymeric microspheres comprise up to 5% by weight of the paste, while the glass and polymeric microspheres together make up to 25% by weight of the paste.

[0036] In a preferred embodiment, the laminate layer of the invention exhibits a relatively low density as well as sufficient strength for the end use. For example, the laminates layer typically has a density of 1.3 g/cm³ or less, and more preferably 1.2 g/cm³ or less.

[0037] Hollow microspheres are commercially available. For example, an expanded polymeric microsphere based on copolymer shells of an acrylonitrile and PVDC coated with calcium carbonate is available from Pierce and Stevens Corp. under the trade name Dualite M6017AE.

[0038] The unsaturated polyester resins contained in the laminate layer, the barrier coat, and optionally the gel coat are well known in the art and available from a variety of commercial sources. They contain an unsaturated monomer and a polyester polymer produced by copolymerization of a polyol component, generally a diol, and a polycarboxylic acid component, generally a dicarboxylic acid. At least part of the polycarboxylic component is made up of an unsaturated carboxylic acid or carboxylic anhydride.

[0039] Styrene is the most commonly used unsaturated monomer, and is preferred. Other unsaturated monomers usable to make polyester resins of the invention include, without limitation, vinyltoluene, methyl methacrylate, diallyl phthalate, α-methylstyrene, triallyl cyanurate, and divinylbenzene.

[0040] Polyol and diol components used to make polyester resin include without limitation propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, propylene oxide, 2,2,4-trimethylpentane-1,3-diol, tetrabromobisphenol dipropoxy ether, 1,4-butanediol, and dicyclopentadiene hydroxyl adducts.

[0041] Saturated dibasic acids or anhydrides include, without limitation, phthalic anhydride, isophthalic acid, adipic acid, chlorendic anhydride, tetrabromophthalic anhydride, tetrahydrophthalic anhydride, terephthalic acid, tetrachlorophthalic anhydride, glutaric acid, and cyclopentadiene-maleic anhydride Diels-Alder adducts. Examples of unsaturated acids or anhydrides include without limitation maleic anhydride, fumaric anhydride, methacrylic acid, acrylic acid, and itaconic acid.

[0042] When the polycarboxylic acid component comprises one of the phthalic, isophthalic, or terephthalic acid derivatives such as those mentioned above, the polyester resin is commonly referred to an “isophthalic resin”, an isophthalic acid resin”, or “isophthalic acid based resin”.

[0043] When the diol or glycol component contains the dicyclopentadiene hydroxyl adducts mentioned above, or when the dicarboxylic acid or anhydride component includes dicyclopentadiene-maleic anhydride Diels-Adler types of adducts, the polyester resins are commonly referred to as dicyclopentadiene resins, or DCPD resins. During the process to make the dicyclopentadiene resins, dicyclopentadiene can dissociate into cyclopentadiene monomer. Both the monomer and the dimer can react with maleic anhydride or other unsaturated acids as well as with the diol components to form resins exhibiting both terminal cycloaliphatic ether and cycloaliphatic dibasic acid groups derived from cyclopentadiene and unsaturated acid ester derivatives.

[0044] In a non-limiting example, to make a DCPD resin, dicyclopentadiene may be added gradually to a reactor in which maleic anhydride and a glycol have been added. Depending on the addition rate and the reactor temperature, dicyclopentadiene initially enters into chain termination reactions with the glycol maleates. At higher temperatures, dicyclopentadiene dissociates into cyclopentadiene and enters into Diels-Adler types of addition reactions with unreacted, unsaturated acid anhydride and with the glycol maleates or other polyester polymer species containing unsaturation.

[0045] Reinforcing fibers are used in the laminate layer and alternatively in the barrier coat of the composites of the invention. The reinforcing fibers in the laminate layer may be selected from the group consisting of glass fibers, carbon fibers, and ceramic fibers. In a preferred embodiment, the fibers in the laminate layer have a length of 6 mm (about ¼ inch) or longer. Preferably, the fiber length is about 12 mm or greater and in a particularly preferred embodiment, the reinforcing fiber has a length of about 25 mm (about 1 inch). Glass fibers are generally preferred because of their lower costs. They are commercially available in the form of glass fiber roving which is composed of many glass bundles. Each bundle in turn is composed of thousands of filaments The filaments have diameters from 5 to 15 micrometers.

[0046] Other conventional additives may be used in formulating the laminate layer and the barrier coat in the composites of the invention. These include, without limitation, solvents, wetting agents, and dispersing additives. Defoamers may be used as air release additives, and thixotropes such as fumed silica may be added to adjust the viscosity. Such additives are well known in formulating cured polyester components and are illustrated in the Examples below.

[0047] The polyester resins of the invention also contain an initiator composition that is capable of initiating cure of the polyester resin compositions at a reasonably low temperature. In preferred embodiment, cure occurs at 50° C. or less. In a particularly preferred embodiment, cure occurs at around room temperature or about 20°-30° C. Generally, the initiator composition includes both an initiator compound and an activator or promoter. The initiator and the activator or promoter work in tandem to kick off initiation at a desired processing temperature. Preferred catalysts or initiators include various organic peroxides and peracids. Particularly preferred are those initiators or catalysts capable of initiating cure at a temperature of about 50° C. or less. Examples include without limitation benzoyl peroxide, methyl ethyl ketone hydroperoxide (MEKP), and cumene hydroperoxide. For the preferred MEKP, activators such as cobalt octoate, cobalt 2-ethylhexanoate, and cobalt naphthenate may be added, resulting in initiator compositions capable of curing the polyester resin at a temperature from about room temperature up to 50° C. Typically, the initiator is held separately from the rest of the composition until the final spray. During spray, the initiator and polyester resin composition are combined, and cure begins. Some commercially available polyester resins include promoters such as the cobalt octoate and cobalt naphthenate mentioned above. In this case it is necessary to provide the initiator catalyst, such as MEKP, separately upon spraying to begin cure of the layer.

[0048] In one embodiment, the invention provides a method for preparing a composite using a spray up operation, comprising the steps of applying a gel coat into a mold, applying a barrier coat over the gel coat, and applying a laminate formula over the barrier coat. The laminate formula preferably contains 40-80% by weight of a paste and 20-60% by weight of reinforcing fibers. The paste contains 70% or more by weight of an unsaturated polyester resin, up to 25% of a filler, and an initiator composition capable of curing the resin at a temperature of 50° C. or lower. In a preferred embodiment, the paste contains up to 25% by weight glass hollow microspheres. In another preferred embodiment, the paste contains 90% or more by weight of an unsaturated polyester resin and up to 5% by weight polymeric hollow microspheres. In another embodiment, the paste contains up to 25% by weight total of glass and polymeric microspheres, with the polymeric microspheres present at up to 5% by weight of the paste. In a preferred embodiment, the gel coat is applied to a thickness of from 0.2 mm to 2 mm, the barrier coat to a thickness of 0.5 to 5 mm, and the laminate layer or layers to a thickness from 1 to 10 mm. In another embodiment, the gel coat is applied to a thickness of about 0.5-1.5 mm, the barrier coat is applied to a thickness of about 0.25 to 2 mm, and the laminate layer is applied to a thickness of about 1 to about 5 mm. In a preferred embodiment, the composite is to be used as an automobile body panel, having a thickness of from 2 to 15 mm, preferably from 2 to 12 mm, more preferably from 3 to 8 mm. In a preferred embodiment, the composite is about 4 mm thick.

[0049] In a preferred embodiment, the laminate layer comprises a laminate composition containing a paste and a filler wherein the paste comprises a low shrink polyester resin such as a dicyclopentadiene resin, up to 5% by weight polymeric hollow microspheres, and an initiator capable of initiating cure at a temperature of 50° C. or less. The laminate composition also contains a filler comprising reinforcing fibers having a length greater than or equal about 6 mm, preferably greater than or equal about 12 mm. In a particularly preferred embodiment, the laminate layer comprises glass fibers of approximately 25 mm (1 inch) in length.

[0050] Composite articles are prepared according to the invention comprising a gel coat layer, a laminate layer and a barrier layer disposed between the gel coat and the laminate.

[0051] In an alternate method, the laminate layer may be applied by hand laying a glass cloth on top of the barrier coat layer in the mold and applying a laminate resin composition to the glass cloth. The laminate resin composition comprises 70% or more by weight of a low shrink polyester resin and up to 25% of glass hollow microspheres or 90% or more by weight resin and up to 5% by weight of polymeric hollow microspheres. In a preferred embodiment, the composite article is used as an automotive body panel. In one embodiment, the maximum thickness of the body panel is about 6 mm and in another preferred embodiment, the maximum thickness of the body panel is about 4 mm.

[0052] The invention has been described above with respect to preferred embodiments. Further non-limiting examples given in the examples that follow.

EXAMPLE 1 Preparation of a Laminate Formulation

[0053] The following components are mixed together to form a laminate formulation. The table gives the amount by weight of each component used. The amounts are expressed as parts by weight of the paste, unless otherwise indicated. As stated earlier, the laminate comprises the paste and fiber. In this Example, the fibers constitute about 38% by weight of the laminate and the balance is the paste. A description of each component follows as well as the method for preparing a laminate paste from the components. Components Parts AOC VX-2190 130 Byk W-972 1.05 Byk R-605 0.30 Byk A-555 0.30 AN bubbles (Dualite, M6017AE) 3.00 Fumed Silica (TS-720) 1.60 MEKP (Aldrich, 32% in DMP) 1.95 Glass Fiber (Certainteed 299) 38%

[0054] AOC VX-2190 is a sprayable unsaturated polyester resin with a styrene monomer content of 32.52%, manufactured by Alpha/Owens-Corning. It contains a dicyclopentadiene resin. A thixotrope has been added by the manufacture to bring its viscosity to a Brookfield viscosity of 670 cps using an RVT viscometer at 20 RPM with a #3 spindle. The component also contains a promoter, cobalt 2-ethylhexanoate. The density is 1.100 g/cc.

[0055] BYK W-972 is a wetting and dispersing additive manufactured by BYK. The density is 1.010 g/cc.

[0056] BYK R-605 is a wetting and dispersing additive manufactured by BYK. It facilitates dispersion during incorporation of fumed silicas. It increases and stabilizes thixotropic behavior. The density is 0.930 g/cc.

[0057] BYK A-555 is an air release additive manufactured by BYK. It is a solution of silicon free, foam destroying polymers with a density of 0.880 g/cc.

[0058] Dualite M6017AE is expanded polymeric microspheres based on copolymer shells of acrylonitrile and PVDC (polyvinylidene chloride) coated with calcium carbonate, manufactured by Pierce and Stevens Corp. The mean particle size is 70 microns, and the density is 0.13 g/cc.

[0059] TS-720 is a fumed silica thixotrope manufactured by Cab-O-Sil. The apparent density is 0.050 g/cc.

[0060] MEKP is a methyl ethyl ketone peroxide solution manufactured by Aldrich. It is a 32% solution in dimethyl phthalate.

[0061] Glass Fiber Certainteed #299 is a glass fiber 299-207-CT manufactured by Certainteed. The average length of the glass fiber is 1 inch. The density is 2.54 g/cc.

[0062] The above components (minus the glass fibers) are mixed as follows to form a paste:

[0063] Liquid VX-2190 resin is weighed into a five-gallon metal can. Thereafter the liquid W-972, R-605, and A-55 are added and stirred slightly with a wooden tongue depressor. The above liquid components are then mixed at 400 RPM for 5 minutes. The polymeric microspheres, Dualite M6017AE are slowly mixed in over a seven minute period. Next the fumed silica, TS-720 is added over a seven minute period. The mixing speed is increased to 700 RPM for about eleven minutes until the paste temperature reaches a temperature of about 26° C. The mixing speed is reduced to 400 RPM and mixing continues for an additional 2 minutes.

[0064] The peroxide initiator, MEKP, is added through the spray gun during part preparation. The gun is also set to deliver 38 parts by weight glass fiber for every 62 parts of the paste.

[0065] The formulation can be adjusted to provide a range of final viscosities to meet the processing requirements. The viscosity of the formula above is about 1290 cps measure at 22° C. using a Brookfield RVT viscometer, spindle number 3 at 20 RPM. In a lab test, an epoxy mold is treated with mold release. Then a 0.5 mm gel coat is applied to the mold and partially cured, followed by a barrier coat of 1.0 mm thickness. After partial curing, a 2.5 mm thick laminate is applied in two steps using the above formulation. In the first step a 1 mm thick laminate is applied and partially cured, followed by a 1.5 mm thick laminate. Following complete cure of all layers, the composite panel is demolded. The composite has an excellent surface appearance.

EXAMPLE 2 Preparation of a Laminate Formulation

[0066] The following components are used in the preferred ranges indicated. Component Density Range Yabang DC-191 1.100 90-100  Byk S 750 0.840 0-1.0 Byk R 605 0.930 0-0.9 Byk A 555 0.880 0-0.5 PBQ (Ashland Mod E—5%) 1.130 0-0.3 Cobalt Naphthenate (8%) 0.950 0.05-0.2   AN Bubbles (Dualite, M6017AE) 0.130 0-5.0 Fumed silica (PTG) 1.800 0-3.0 Black (CM-2015) 1.24  0-0.5

[0067] Yabang DC-191 is a sprayable unsaturated polyester resin with a styrene monomer content of 29.76% manufactured by Yabang in China. It is a fumaric acid based polyester containing dicyclopentadiene, dimethylstyrene, and dicyclopentyl alcohol. There is no promoter or thixotrope. The Brookfield viscosity is 378 cps using an RVT viscometer at 20 RPM with a #2 spindle. The resin contains the promoter, cobalt naphthenate.

[0068] S-750 is a combination of waxes with polar components, manufactured by BYK. It is used as a styrene emission suppressant developed specially for DCPD resins.

[0069] R-605 is a wetting and dispersing additive to facilitate dispersion during incorporation of fumed silicas. It is manufactured by BYK.

[0070] A-555 is a solution of silicone free foam-destroying polymers that acts as an air release additive, manufactured by BYK.

[0071] Modifier E is an inhibitor solution of 4.99 weight percent para-benzoquinone in diallyl phthalate, manufactured by Ashland Chemical Co.

[0072] Cobalt naphthenate is a promoter for polyester resins manufactured by Sigma Chemical Co. It is 8% by weight cobalt.

[0073] Dualite M6017AE is expanded polymeric microspheres manufactured by Pierce and Stevens.

[0074] CM-2015 black is a colorant manufactured by Plasticolors.

[0075] PTG is an untreated fumed silica thixotrope manufactured by Cab-O-Sil.

[0076] Delta X-9 is methyl ethyl ketone peroxide solution manufactured by Elf Atochem NA

[0077] Glass Fiber #299-207-CT is a 1 inch glass fiber manufactured by Certainteed.

[0078] A low density laminate paste may be formulated as follows:

[0079] Liquid Yabang DC-191 polyester resin is weighed into a 5 gallon can. The liquid S-750 wax is first mixed well in its container and then weighed into a smaller container. The polyester resin is stirred at 400 RPM while the wax is slowly added. Mixing continues for a total of 10 minutes and stopped.

[0080] The liquid R-605 and liquid A-555 is weighed into the can of the polyester resin mixture and stirred slightly with a wooden tongue depressor. The liquid modifier E, weighed earlier in a syringe, is added and stirred slightly with a wooden tongue depressor. The 5 gallon can is now positioned under a mixer and a mixing blade attached. The liquid components are mixed at 400 RPM for 5 minutes.

[0081] The liquid cobalt naphthenate, weighed earlier in a syringe, is added while mixing continues for a total of 5 minutes. The polymeric microspheres, Dualite M6017AE are slowly mixed in over a 5 minute period. The black colorant CM-2015 is mixed in over a 3 minute period. While continuing stirring at 400 RPM, the filmed silica is slowly added over a 4 minute period. After all the fumed silica is added, the mixing speed is increased to 700 RPM for about 6 minutes until the paste reaches a temperature of about 26° C. The total time of mixing until the paste reaches this temperature varies depending on the ambient temperature. Then the mixing speed is reduced to 400 RPM and mixing is stopped after 2 additional minutes. The total mixing time is about 30 minutes.

[0082] A peroxide initiator (Delta X-9) is added to the spray gun during part preparation. The gun is also set to deliver the glass fibers simultaneous with application of the paste and initiator.

EXAMPLES 3-5

[0083] Laminate formulations are put together with the ingredients indicated below, according to the general procedures described in Example 1 and 2. In all examples, the MEKP and the glass fibers are added through the spray gun during part preparation.

Example 3

[0084] Component Parts Yabang DC-191 100.00 Byk S 750 1.00 Byk R 605 0.23 Byk A 555 0.23 PBQ (Ashland Mod E—5%) 0.110 Cobalt Naphthenate (8%) 0.090 AN Bubbles (Dualite, M6017AE) 2.31 Fumed silica (PTG) 0.57 Black (CM-2015) 0.05 MEKP (Delta X-9) 2.3 Glass Fiber (Certainteed 299) 52.37

Example 4

[0085] Component Parts AOC VX-2190 100.00 Byk S 750 1.00 Byk R 605 0.23 Byk A 555 0.23 PBQ (Ashland Mod E—5%) 0.110 Cobalt Naphthenate (8%) 0.090 Glass microspheres K46 (3M) 10.50 Fumed silica (PTG) 0.31 Black (CM-2015) 0.05 MEKP (Delta X-9) 2.2 Glass Fiber (Certainteed 299) 52.37

Example 5

[0086] Component Parts Yabang DC-191 100.00 Byk R 605 0.23 Byk A 555 0.23 PBQ (Ashland Mod E—5%) 0.110 Cobalt Naphthenate (8%) 0.090 AN Bubbles (Dualite, M6017AE) 2.31 Glass microspheres K46 (3M) 10.50 Fumed silica (PTG) 0.57 Black (CM-2015) 0.05 MEKP (Delta X-9) 2.3 Glass Fiber (Certainteed 299) 43.51

EXAMPLE 6

[0087] A barrier coat composition is formulated as follows. Components Parts AOC VX-2190 100 Byk W 972 0.81 Glass Bubbles (3M, K46/4000) 21.00 Milled Glass Fiber (OCF {fraction (1/64)}″) 41.42 Fumed Silica (TR-720) 0.61 MEKP (Aldrich, 32% in DMP) 1.95 Total 165.79

[0088] Glass Bubbles (3M, K46/4000) are glass hollow microspheres sold by 3M.

[0089] Milled Glass Fiber is glass fibers of 5-10 micrometers in diameter and an average length of {fraction (1/64)}″, available commercially from Owens Corning.

[0090] Other materials are as listed in Example 1.

[0091] The formulation can be adjusted to provide a range of final viscosities to meet processing requirements. In a lab test, a glass plate is treated with mold release for ease of demolding. Then a 0.5 mm gel coat is applied on the glass plate and partially cured. A barrier coat layer of 0.5 mm thickness is then applied containing the components listed above. After partial cure of the barrier coat a 3 mm thick laminate is applied in two steps. In the first step a 1 mm thick laminate is applied and partially cured followed by a 2 mm thick laminate. The laminate is a polyester resin reinforced with 25% by weight chopped fibers. After complete cure of all layers at room temperature the plaque is demolded. The surface is smooth and free of fiber read through. A similar process with no barrier coat is conducted and the resultant plaque shows extensive fiber read through. The thickness of the barrier coat may need to be adjusted depending on the processing conditions, the chemistry and the thickness of the gel coat and the laminate.

EXAMPLE 7

[0092] Formulation of a Barrier Coat Component density, g/cm³ Range Yabang DC-191 1.100 75-100  Eterset 2110-1 1.100 0-25  Styrene Monomer 0.907 0-10  Byk W 972 1.010 0-1.0 Byk R 605 0.930 0-0.9 Byk A 555 0.880 0-0.5 PBQ (Ashland Mod E-5%) 1.130 0-0.3 AN Bubbles (Dualite, M6017AE) 0.130 0-5.0 Glass bubbles (3M, K37) 0.37  0-5.0 Cobalt Naphthenate (8%) 0.950 0.05-0.2   N,N-Dimethylaniline 0.956 0-0.3 Med Teal Blue (CF-31977) 1.500 0-0.3 Milled Glass Fiber (OCF {fraction (1/64)}″) 2.540 >0-30    Fumed silica (PTG) 1.800 0-3.0

[0093] Yabang DC-191, Byk R 605, Byk A 555, PBQ, AN Bubbles, Cobalt naphthenate, and fumed silica are as defined in Example 2.

[0094] Eterset 2110-1 is a flexible phthalic acid based polyester resin manufactured by Eternal Chemical Company, Taiwan. It contains no promoter or thixotrope. It has a styrene monomer content of 23.26%, a viscosity of 2384 cps using an RVT viscometer at 10 RPM with a #2 spindle.

[0095] Styrene monomer, manufactured by J. T. Baker, has a density of 0.907.

[0096] BYK W-972 is a wetting and dispersing additive manufactured by BYK. The density is 1.010 g/cc.

[0097] Glass Bubbles (3M, K37) are glass hollow microspheres sold by 3M.

[0098] N,N-Dimethylaniline is a tertiary amine used as an accelerator, manufactured by EM Science.

[0099] Medium teal blue is a colorant manufactured by Plasticolors, Inc. Colorants are used to differentiate the barrier coat from the gel coat. It is used to help the spray/chop operator spray a more uniform barrier coat thickness.

[0100] Milled glass fiber is 737-BC {fraction (1/64)} inch, manufactured by Owens-Corning.

[0101] PTG is an untreated fume silica thixotrope manufactured by Cab-O-Sil.

[0102] Delta X-9 is a methyl ethyl ketone peroxide solution manufactured by Elf Atochem.

[0103] A barrier coat composition is formulated from the above components as follows.

[0104] The liquid Yabang DC-191 polyester resin is weighed into a 5 gallon metal can. The Eterset 2110-1 polyester resin weighed into the can and stirred slightly with a wooden tongue depressor. The styrene monomer, W-972, W-605, and A-555 are weighed into the can and stirred slightly with a wooden tongue depressor.

[0105] Liquid Modifier E, weighed earlier in a syringe, is added and stirred slightly with a wooden tongue depressor. The 5 gallon can is positioned under a mixer and the mixer blade is attached.

[0106] About 50-60 grams of the Dualite M6017AE polymeric bubbles are added to the liquid component. Then the mixer is turned on and the combination mixed at 400 RPM for about 1 minute. The balance of the polymeric bubbles is added over an additional 9 minute mixing period.

[0107] The medium blue teal colorant is then mixed in over a 2 minute period. The liquid cobalt naphthenate, weighed earlier in a syringe, is added over a 2 minute period. Then the dimethylaniline, weighed earlier in a syringe, is mixed in over a 2 minute period.

[0108] Mixing continues at 400 RPM while the milled glass fiber is added during a 5 minute period. Finally the fumed silica is slowly added over a 7 minute period.

[0109] The mixing speed is increased to 700 RPM for about 7 minutes or until the paste reaches a temperature of 29° C. The mixing time varies depending on the ambient temperature. The mixing speed is reduced to 400 RPM and stopped after an additional 2 minutes of mixing. The total mixing time is about 37 minutes. Delta X-9 peroxide initiator is added to the spray gun during part preparation at a treatment level of about 1-2%.

EXAMPLES 8-10

[0110] Barrier coats are formulated according to Example 2, with the following ingredients.

Example 8

[0111] Component Parts Yabang DC-191 77.5 Eternal 2110-1 22.5 Styrene Monomer 5 Byk W 972 0.81 Byk W 605 0.6 Byk A 555 0.23 PBQ (Ashland Mod E—5%) 0.044 AN Bubbles (Dualite, M6017AE) 4.8 Cobalt Naphthenate (8%) 0.1 N,N-Dimethylaniline 0.2 Med Teal Blue (CF-31977) 0.03 Milled Glass Fiber (OCF {fraction (1/64)}″) 30 Fumed silica (PTG) 3 MEKP (Delta X-9) 2.2

Example 9

[0112] Yabang DC-191 90.5 Eternal 2110-1 9.95 Byk W 972 0.81 Byk A 555 0.23 PBQ (Ashland Mod E—5%) 0.05 AN Bubbles (Dualite, M6017AE) 4.2 Cobalt Naphthenate (8%) 0.1 N,N-Dimethylaniline 0.2 Med Teal Blue (CF-31977) 0.03 Milled Glass Fiber (OCF {fraction (1/64)}″) 25 Fumed silica (PTG) 2.5 MEKP (Delta X-9) 2.2

Example 10

[0113] AOC VX2190 91.2 Byk W 972 0.81 PBQ (Ashland Mod E—5%) 0.05 AN Bubbles (Dualite, M6017AE) 3.5 Glass microspheres K46 (3M) 15 Cobalt Naphthenate (8%) 0.1 N,N-Dimethylaniline 0.2 Med Teal Blue (CF-31977) 0.03 Milled Glass Fiber (OCF {fraction (1/64)}″) 20 Fumed silica (PTG) 2.7 MEKP (Delta X-9) 2.2

EXAMPLE 11 Preparation of A Composite Article

[0114] A gel coat composition is sprayed into a mold to a desired thickness. Next a barrier coat composition, such as those in Examples 6-10, is applied in the mold over the gel coat. Next, a laminate formulation, such as described in Examples 1-5, is applied as follows.

[0115] An operator hooks up a spray gun, such as are commercially available from Magnum in Florida, to a bucket containing a paste, a second bucket containing a solution of the cure initiator, and a source of fiber glass rovings. On operation of the gun, the paste and the initiator are combined and sprayed onto the barrier coat in the mold. At the same time the glass rovings are advanced through a cutter to deliver 1″ glass fibers that meet the solution of paste and initiator in mid-air and fall on the barrier coat in the mold. The operator continues to operate the gun with spraying in a side-to-side motion until the desired thickness of build up of the laminate applied in the mold is obtained. Thereafter, the composite is allowed to cure in the mold, followed by demolding of the article. Cure may be carried out at room temperature or up to about 50° C. Depending on the temperature, the cure time may range from several minutes to several hours to up to a day.

[0116] The description of the invention is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention, which are defined in the dependent claims. 

What is claimed is:
 1. A method for preparing a composite by spray up operation, comprising the steps of: applying a gel coat into a mold; applying a barrier coat over the gel coat; and applying a laminate formula over the barrier coat, wherein the laminate formula comprises 40-80% by weight paste and 20-60% by weight reinforcing fibers, wherein the paste comprises 70% or more by weight resin, up to 25% by weight filler, and an initiator composition; wherein the resin comprises an unsaturated polyester resin curable at a temperature of 50° C. or lower; the filler comprises particles having a density lower than that of the resin, and the initiator composition contains an optional promoter or accelerator, the initiator composition being capable of initiating cure of the resin at a temperature of 50 C or lower.
 2. A method according to claim 1, wherein the gel coat is 0.2-2 mm thick, the barrier coat is 0.5-5 mm thick, and the laminate is 1-10 mm thick.
 3. A method according to claim 1, wherein the thickness of the composite is from 2-15 mm.
 4. A method according to claim 1, wherein the composite is an automobile body panel.
 5. A method according to claim 1, wherein the filler comprises glass hollow microspheres.
 6. A method according to claim 1, wherein the filler comprises polymeric hollow microspheres.
 7. A method according to claim 1, wherein the paste comprises 90% or more by weight resin and up to 5% by weight polymeric hollow microspheres.
 8. A method according to claim 6, wherein the polymeric hollow microspheres are coated with calcium carbonate.
 9. A method according to claim 1, wherein applying the laminate formula comprises operating a spray gun in a side-to-side motion until a desired thickness of laminate is obtained.
 10. A laminate composition comprising a paste and filler, wherein the paste comprises, a dicyclopentadiene unsaturated polyester resin; polymeric hollow microspheres; and an initiator composition capable of initiating curing at a temperature of 50° C. or less, and wherein the filler comprises reinforcing fibers having a length greater than or equal about 6 mm.
 11. A composition according to claim 10, wherein the reinforcing fibers comprise glass fibers having a length greater than or equal about 12 mm.
 12. A composition according to claim 10, wherein the reinforcing fibers comprise glass fibers of weight approximately 25 mm.
 13. A composition according to claim 10, wherein the paste comprises 90% or more by weight resin and up to 5% by weight polymeric hollow microspheres.
 14. A composition according to claim 10, wherein the microspheres are coated with calcium carbonate.
 15. A composition according to claim 10, wherein the density of the laminate layer after cure is 1.2 g/cm³ or less.
 16. A composite article comprising a gel coat layer, a laminate layer, and a barrier layer disposed between the gel coat and laminate, wherein the laminate layer comprises 40-80% by weight paste and 20-60% by weight reinforcing fibers, wherein the paste comprises 70% or more by weight of an unsaturated polyester resin curable at a temperature of 50° C. or lower; up to 25% of a filler comprising particles having a density lower than that of the resin; and an initiator composition capable of initiating cure of the resin at a temperature of 50° C. or lower.
 17. A composite article according to claim 16, wherein the composite article comprises an automobile body panel.
 18. An article according to claim 16, wherein the total thickness of the article is 2-12 mm.
 19. An article according to claim 16, wherein the total thickness of the article is 3-8 mm, the thickness of the gel coat is 0.5-1.5 mm, the thickness of the barrier coat is 0.75-2 mm, and the thickness of the laminate layer is 1-5 mm.
 20. An article according to claim 16, wherein the filler comprises polymeric hollow microspheres.
 21. An article according to claim 16, wherein the laminate and the barrier layer comprise cured unsaturated polyester resins, and the gel coat comprises a cured thermoset resin.
 22. An article according to claim 16, wherein the reinforcing fibers comprise glass fibers having a length of 6 mm or greater.
 23. An article according to claim 22, wherein the glass fibers are greater than or equal to about 12 mm in length.
 24. An article according to claim 22, wherein the glass fibers are about 25 mm long.
 25. An article according to claim 16, wherein the laminate layer comprises a cured dicyclopentadiene unsaturated polyester resin.
 26. An article according to claim 16, wherein the density of the laminate layer is 1.2 g/cm³ or less.
 27. An article according to claim 16, wherein the paste comprises 80% or more by weight resin and up to 10% by weight glass hollow microspheres.
 28. An article according to claim 16, wherein the filler is selected from the group consisting of glass hollow microspheres, polymeric hollow microspheres, and mixtures thereof.
 29. An article according to claim 16, wherein the paste comprises up to 5% by weight of polymeric hollow microspheres.
 30. A method for making a multilayer composite, comprising the steps of: applying a gel coat layer to a mold surface; applying a barrier coat layer onto the gel coat in the mold; hand laying a glass cloth on top of the barrier coat layer; and applying a laminate resin composition to the glass cloth, wherein the laminate resin composition comprises 70% or more by weight of an unsaturated polyester resin and up to 25% by weight hollow microspheres.
 31. A method according to claim 30, further comprising curing the composite at a temperature of 50° C. or less.
 32. A method according to claim 30, further comprising curing the composite at a temperature of 30° C. or less.
 33. A method according to claim 30, wherein the polyester resin comprises a dicyclopentadiene polyester resin.
 34. A method according to claim 30, wherein the laminate resin composition comprises 90% or more by weight polyester resin and up to 5% by weight polymeric hollow microspheres.
 35. A method according to claim 34, wherein the polyester comprises a dicyclopentadiene resin.
 36. An automobile body panel, comprising a cured multilayer composite article comprising: a gel coat layer; a laminate layer; and a barrier layer disposed between the gel coat layer and the laminate layer, wherein the laminate layer comprises reinforcing glass fibers in a matrix of a cured polyester resin, wherein the matrix comprises up to 5% by weight of polymeric hollow microspheres and the polyester resin comprises a dicyclopentadiene polyester resin.
 37. A body panel according to claim 36, wherein the glass fibers are greater than or equal to about 12 mm in length.
 38. An automobile body panel according to claim 36, wherein the maximum thickness of the body panel is about 6 mm.
 39. An automobile body panel according to claim 36, wherein the maximum thickness of the body panel is about 4 mm. 